Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 18

April 25, 2014

Volume 53, Issue 18

Pages 4497–4724

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. You have free access to this content
      Cover Picture: An Efficient and Modular Route to Sequence-Defined Polymers Appended to DNA (Angew. Chem. Int. Ed. 18/2014) (page 4497)

      Thomas G. W. Edwardson, Dr. Karina M. M. Carneiro, Dr. Christopher J. Serpell and Prof. Hanadi F. Sleiman

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201401123

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      Sequence-controlled polymers attached to DNA can be prepared by solid-phase phosphoramidite coupling, as H. F. Sleiman, C. J. Serpell, and co-workers report in their Communication on page 4567 ff. Polymers with the same molecular composition but different monomer patterns exhibit different amphiphilic self-assembly. As the DNA component still retains base-pairing fidelity, these novel conjugates encode information in two distinct, and orthogonal, assembly languages.

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      Inside Cover: The Formation and Self-Assembly of Long Prebiotic Oligomers Produced by the Condensation of Unactivated Amino Acids on Oxide Surfaces (Angew. Chem. Int. Ed. 18/2014) (page 4498)

      Prof. Gianmario Martra, Dr. Chiara Deiana, Dr. Yuriy Sakhno, Ilvis Barberis, Marco Fabbiani, Dr. Marco Pazzi and Prof. Marco Vincenti

      Version of Record online: 2 APR 2014 | DOI: 10.1002/anie.201401130

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      The formation of long polypeptides from unactivated glycine adsorbed on SiO2 and TiO2 and the self-assembly of these polymers into both helical and β-sheet-like patches following surface hydration is reported by G. Martra et al. in their Communication on page 4671 ff. These results shed light on the formation of polymers from small biomolecules under abiotic conditions, thus adding to our understanding of the basis of biochemical complexity and the prebiotic formation of biopolymers.

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      Inside Back Cover: Peapod-Type Nanocomposites through the In Situ Growth of Gold Nanoparticles within Preformed Hexaniobate Nanoscrolls (Angew. Chem. Int. Ed. 18/2014) (page 4725)

      Dr. Shiva Adireddy, Cecilia E. Carbo, Taha Rostamzadeh, Dr. Jose M. Vargas, Prof. Leonard Spinu and Prof. John B. Wiley

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201401116

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      Peapod nanocomposites can be readily fabricated by the in situ growth of gold within scrolled nanosheets or partially filled Fe3O4 hexaniobate nanopeapods. In their Communication on page 4614 ff., J. B. Wiley et al. report the synthesis and characterization of both gold and gold–Fe3O4 hexaniobate nanopeapods. The composites show variation in optical and magnetic properties as a function of composition.

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      Back Cover: Formation of [Bi11]3−, A Homoatomic, Polycyclic Bismuth Polyanion, by Pyridine-Assisted Decomposition of [GaBi3]2− (Angew. Chem. Int. Ed. 18/2014) (page 4726)

      Dipl.-Chem. Bastian Weinert, Armin Rainer Eulenstein, Dr. Rodica Ababei and Prof. Dr. Stefanie Dehnen

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201401121

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      With its so-called ufosan structure the [Bi11]3− ion is the first polycyclic bismuth polyanion. S. Dehnen and co-workers show in their Communication on page 4704 ff. that its synthesis occurs by the surprisingly simple reaction of [K([2.2.2]crypt)]2(GaBi3) with the pyridine solvent to yield [K([2.2.2]crypt)]3(Bi11). The binary Zintl anion [GaBi3]2− decomposes under oxidative coupling of pyridine molecules and release of H2 to form the [Bi11]3− species.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. You have free access to this content
      Frontispiece: Self-assembled Dynamic 3D Fingerprints in Liquid-Crystal Coatings Towards Controllable Friction and Adhesion

      Dr. Danqing Liu and Dr. Dirk J. Broer

      Version of Record online: 25 APR 2014 | DOI: 10.1002/anie.201481871

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      D. Liu and D. J. Broer show in their Communication on page 4542 ff. that artificial fingerprints can be switched between a flat state and a protruding state. The resulting friction changes allow use in a robot-like gripper.

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
  4. News

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
  5. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Dunwei Wang (page 4518)

      Version of Record online: 22 JAN 2014 | DOI: 10.1002/anie.201310780

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      “If I were not a scientist, I would be a fiction writer. My favorite food is fruit salad …” This and more about Dunwei Wang can be found on page 4518.

  6. News

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
  7. Book Review

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Orbital Interactions in Chemistry. 2nd Edition. By Thomas A. Albright, Jeremy K. Burdett and Myung Hwan Whangbo. (pages 4520–4521)

      Santiago Alvarez

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/anie.201311146

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      John Wiley & Sons, Hoboken, 2013. 834 pp., hardcover, € 135.60.—ISBN 978-0471080398

  8. Highlights

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Dimeric Natural Products

      Double Trouble—The Art of Synthesis of Chiral Dimeric Natural Products (pages 4524–4526)

      Tim Wezeman, Dr. Kye-Simeon Masters and Prof. Dr. Stefan Bräse

      Version of Record online: 3 APR 2014 | DOI: 10.1002/anie.201402384

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      Double or nothing! Recently the total synthesis of secalonic acids A and D was reported. This work and other natural product syntheses with a dimerization step as a common feature are featured in this Highlight. The significant biological activity of the secalonic acids and the fact that their synthesis has fascinated synthetic chemists for the past forty years make this work a milestone in natural product synthesis.

    2. Hydrogen Storage

      CO2 Fixation through Hydrogenation by Chemical or Enzymatic Methods (pages 4527–4528)

      Prof. Matthias Beller and Prof. Uwe T. Bornscheuer

      Version of Record online: 6 APR 2014 | DOI: 10.1002/anie.201402963

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      Two birds with one stone: The simulaneous fixation of the greenhouse gas carbon dioxide and storage of the alternative fuel hydrogen can be accomplished with the formation of formic acid. In principle, this is now possible either with an enzymatic system based on a newly discovered bacterial hydrogen-dependent carbon dioxide reductase or by using organometallic catalysts at room temperature and ambient pressure.

  9. Review

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Metal–Organic Frameworks

      Solvent-Assisted Linker Exchange: An Alternative to the De Novo Synthesis of Unattainable Metal–Organic Frameworks (pages 4530–4540)

      Olga Karagiaridi, Dr. Wojciech Bury, Dr. Joseph E. Mondloch, Prof. Dr. Joseph T. Hupp and Prof. Dr. Omar K. Farha

      Version of Record online: 20 MAR 2014 | DOI: 10.1002/anie.201306923

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      Changing pillars: Solvent-assisted linker exchange (SALE) has gained a lot of attention as a novel synthetic pathway toward metal–organic frameworks (MOFs) that are challenging to access de novo. This Review analyzes the recent advances in the application of SALE and provides a critical assessment of the studies that have facilitated our understanding of this invaluable tool for the development of new MOFs.

  10. Communications

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Smart Materials

      Self-assembled Dynamic 3D Fingerprints in Liquid-Crystal Coatings Towards Controllable Friction and Adhesion (pages 4542–4546)

      Dr. Danqing Liu and Dr. Dirk J. Broer

      Version of Record online: 11 MAR 2014 | DOI: 10.1002/anie.201400370

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      Science friction: Artificial fingerprints are switched between a flat “off” state and a protruding “on” state. The switching principle is based on a modulated change of liquid-crystal chiral-nematic order, thus creating geometric changes. When illuminated with UV light, the 3D fingerprints are activated by azobenzene and appear in the coating. The surface friction decreases when the fingerprints form and increases when they are switched off.

    2. Tropospheric Chemistry

      You have full text access to this OnlineOpen article
      Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications (pages 4547–4550)

      Dr. Oliver Welz, Dr. Arkke J. Eskola, Dr. Leonid Sheps, Dr. Brandon Rotavera, Dr. John D. Savee, Dr. Adam M. Scheer, Dr. David L. Osborn, Dr. Douglas Lowe, Dr.  A. Murray Booth, Ping Xiao, Dr.  M. Anwar H. Khan, Prof. Carl J. Percival, Prof. Dudley E. Shallcross and Dr. Craig A. Taatjes

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201400964

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      Gas-phase reactions: Direct measurements reveal that rate coefficients for reactions of Criegee intermediates with carboxylic acids are substantially larger than previously assumed. Using these new values, modeling suggests that these reactions can be major sinks both for Criegee intermediates and carboxylic acids in the atmosphere.

    3. Biosensing

      Real-Time In Vivo Quantitative Monitoring of Drug Release by Dual-Mode Magnetic Resonance and Upconverted Luminescence Imaging (pages 4551–4555)

      Dr. Jianan Liu, Dr. Jiwen Bu, Prof. Wenbo Bu, Dr. Shengjian Zhang, Dr. Limin Pan, Dr. Wenpei Fan, Dr. Feng Chen, Prof. Liangpin Zhou, Prof. Weijun Peng, Prof. Kuaile Zhao, Prof. Jiulin Du and Prof. Jianlin Shi

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201400900

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      Lighting up drug delivery: Multifunctional Gd core/hollow mesoporous silica shell nanoparticles were synthesized. With doxorubicin (DOX) fully loaded inside the nanoparticles, the upconverted luminescence (UCL) signals are quenched through luminescence resonance energy transfer (LRET), and the longitudinal relaxation time magnetic resonance (T1-MR) signals are almost undetectable. Upon drug release, both the UCL and T1-MR signals are restored. As a result, drug release can be detected by the designed dual-mode nanosensor (see figure; R1: longitudinal relaxivity).

    4. Systems Chemistry

      Selective Encapsulation and Sequential Release of Guests Within a Self-Sorting Mixture of Three Tetrahedral Cages (pages 4556–4560)

      Dr. Azucena Jiménez, Dr. Rana A. Bilbeisi, Dr. Tanya K. Ronson, Dr. Salvatore Zarra, Craig Woodhead and Dr. Jonathan R. Nitschke

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201400541

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      Well sorted: Three discrete metal–organic cages were prepared through the one-pot reaction of five subcomponents, that is, three amines, 2-formylpyridine, and a ZnII salt. Each cage selectively accommodates a single guest within a mixture of three guests, and each guest can be sequentially released following the addition of a chemical stimulus.

    5. Flexible Conducting Materials

      Macroscopic Free-Standing Hierarchical 3D Architectures Assembled from Silver Nanowires by Ice Templating (pages 4561–4566)

      Dr. Huai-Ling Gao, Dr. Liang Xu, Fei Long, Zhao Pan, Yu-Xiang Du, Dr. Yang Lu, Dr. Jin Ge and Prof. Dr. Shu-Hong Yu

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/anie.201400457

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      Silver lining: Macroscopic free-standing hierarchical 3D architectures can be directly built from monodispersed silver nanowires (AgNW) through a general, versatile ice-template assembly technique without using any extra functionalization agents or crosslinking agents. The 3D nanowire monoliths have a binary-network microstructure which provides them with a high electrical conductivity, and, when impregnated with PDMS, great mechanical flexibility.

    6. Sequence-Defined Polymers

      An Efficient and Modular Route to Sequence-Defined Polymers Appended to DNA (pages 4567–4571)

      Thomas G. W. Edwardson, Dr. Karina M. M. Carneiro, Dr. Christopher J. Serpell and Prof. Hanadi F. Sleiman

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/anie.201310937

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      Bilingual: A stepwise solid-phase synthesis approach provides easy access to sequence-controlled polymers attached to DNA. Polymers with the same molecular composition but different monomer patterns exhibit different amphiphilic self-assembly. The DNA component still retains base-pairing fidelity, and thus one molecule “speaks” two orthogonal and programmable assembly languages.

    7. White-Light Emission

      Bright White-Light Emission from a Single Organic Compound in the Solid State (pages 4572–4577)

      Dr. Qing-Yuan Yang and Prof. Dr. Jean-Marie Lehn

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/anie.201400155

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      A bright idea: Remarkably simple organic molecules, based on two 4-pyridone head groups located at the termini of a polymethylene chain, emit bright white light in the solid state. The emission band, which results from excited monomer molecules and stacked excimers, is almost flat over the visible range. Incorporation into a polymeric material gives white-light-emitting films, a feature of potential applied interest.

    8. Transmembrane Channels

      Voltage-Driven Reversible Insertion into and Leaving from a Lipid Bilayer: Tuning Transmembrane Transport of Artificial Channels (pages 4578–4581)

      Wen Si, Prof. Zhan-Ting Li and Prof. Jun-Li Hou

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/anie.201311249

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      Controlling transport: A voltage can drive positively charged channel molecules to insert into or leave from a lipid bilayer (see picture), thus switching on and off the transmembrane transport of K+ ions. The insertion and leaving processes can be tuned by adjusting the direction and strength of the voltage.

    9. Perovskite Catalysts

      A Bifunctional Perovskite Catalyst for Oxygen Reduction and Evolution (pages 4582–4586)

      Dr. Jae-Il Jung, Dr. Hu Young Jeong, Jang-Soo Lee, Dr. Min Gyu Kim and Prof. Dr. Jaephil Cho

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/anie.201311223

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      The perovskite La0.3(Ba0.5Sr0.5)0.7Co0.8Fe0.2O3−δ (La0.3-5582) is introduced as a bifunctional catalyst to compete with precious-metal-based catalysts. The newly introduced perovskite bears rhombohedral phase LaCoO3−δ particles on the surface of the grains.

    10. Emissive Tellurophenes

      Coaxing Solid-State Phosphorescence from Tellurophenes (pages 4587–4591)

      Dr. Gang He, William Torres Delgado, Devon J. Schatz, Dr. Christian Merten, Arash Mohammadpour, Lorenz Mayr, Michael J. Ferguson, Robert McDonald, Prof. Dr. Alex Brown, Prof. Dr. Karthik Shankar and Prof. Dr. Eric Rivard

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201307373

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      Light at the end of the tunnel: By incorporating pinacolboronate side groups, the first examples of tellurophenes that are phosphorescent in the solid state were isolated. These tellurophenes readily form phosphorescent films from solution, making them amenable to device fabrication methods.

    11. Selective Sorption

      You have full text access to this OnlineOpen article
      Shape Selectivity by Guest-Driven Restructuring of a Porous Material (pages 4592–4596)

      Dr. J. E. Warren, C. G. Perkins, Dr. K. E. Jelfs, Dr. P. Boldrin, Dr. P. A. Chater, Dr. G. J. Miller, Dr. T. D. Manning, Dr. M. E. Briggs, Dr. K. C. Stylianou, Dr. J. B. Claridge and Prof. M. J. Rosseinsky

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/anie.201307656

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      Nobody′s perfect: The metal-organic framework Ce(HTCPB) is structurally mismatched to both the para and meta isomers of xylene. It restructures synergically around the para isomer to give a high-quality structural and functional fit, but rearrangement around the meta isomer requires larger host distortions and gives a poorer fit than in the para case. This “off-target” host thus has high selectivity for the sorption of para- over meta-xylene.

    12. Electroactive Platforms

      An Electroactive Biotin-Doped Polypyrrole Substrate That Immobilizes and Releases EpCAM-Positive Cancer Cells (pages 4597–4602)

      SeungHyun Jeon, Dr. Jeong-Mi Moon, Dr. Eun Sook Lee, Dr. Yon Hui Kim and Dr. Youngnam Cho

      Version of Record online: 20 MAR 2014 | DOI: 10.1002/anie.201309998

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      An electroactive anti-EpCAM-immobilized, biotin-doped polypyrrole (Ppy) has been developed as a unique platform for the efficient capture and release of target cancer cells. Biotin-doped Ppy is ideal for damage-free selective cell release using weak electric stimulation. This approach is promising for use in both basic and clinical cancer-related applications.

    13. Photochromism

      Separation of Photoactive Conformers Based on Hindered Diarylethenes: Efficient Modulation in Photocyclization Quantum Yields (pages 4603–4607)

      Wenlong Li, Changhong Jiao, Dr. Xin Li, Prof. Dr. Yongshu Xie, Prof. Dr. Keitaro Nakatani, Prof. Dr. He Tian and Prof. Dr. Weihong Zhu

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201310438

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      Large hindrance, high efficiency: A novel benzobis(thiadiazole)-bridged diarylethene system shows excellent thermal bistability and extremely high, solvent-independent photocyclization quantum yields (Φo-c, up to 90.6 %). It is characterized by a complete separation of the anti-parallel conformer and the suppression of intramolecular charge transfer (ICT). EWG=electron-withdrawing group.

    14. Reaction Dynamics

      Gas-Phase Synthesis of the Benzyl Radical (C6H5CH2) (pages 4608–4613)

      Dr. Beni B. Dangi, Dr. Dorian S. N. Parker, Dr. Tao Yang, Prof. Ralf I. Kaiser and Prof. Alexander M. Mebel

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201310612

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      Do cross the streams! Ab initio electronic structure calculations and crossed molecular beam experiments on the reaction of dicarbon with isoprene are presented. The picture shows a flux contour map of the reaction of dicarbon with isoprene that forms the benzyl radical and atomic hydrogen at a collision energy of 43 kJ mol−1.

    15. Bifunctional Nanopeapods

      Peapod-Type Nanocomposites through the In Situ Growth of Gold Nanoparticles within Preformed Hexaniobate Nanoscrolls (pages 4614–4617)

      Dr. Shiva Adireddy, Cecilia E. Carbo, Taha Rostamzadeh, Dr. Jose M. Vargas, Prof. Leonard Spinu and Prof. John B. Wiley

      Version of Record online: 12 MAR 2014 | DOI: 10.1002/anie.201310834

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      Like peas in a pod: A facile in situ method for Au nanoparticle (NP) growth in nanoscrolls is applied to the formation of plasmonic Au@hexaniobate and bifunctional plasmonic-magnetic Au-Fe3O4@hexaniobate nanopeapods (NPPs). Using a solvothermal treatment, rigid multiwalled hexaniobate nanoscrolls and partially filled Fe3O4@hexaniobate NPPs were formed and used as templates for the Au NPs.

    16. Photocatalysis

      Pigment–Acceptor–Catalyst Triads for Photochemical Hydrogen Evolution (pages 4618–4622)

      Kyoji Kitamoto and Prof. Ken Sakai

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/anie.201311209

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      Electron harvesting: Photo-hydrogen-evolving molecular devices showing substantially improved turnover numbers have been developed by introducing multiviologen tethers into a [PtCl2(2,2′-bipyridine)]-based moiety serving as a light-harvesting and H2-evolving center (see scheme). The improved photocatalytic performance is attributed to the rapidly regenerating character of the pigment due to intramolecular electron transfer from the pigment to the electron reservoirs.

    17. Protected Noble Metal Clusters

      Balancing the Rate of Cluster Growth and Etching for Gram-Scale Synthesis of Thiolate-Protected Au25 Nanoclusters with Atomic Precision (pages 4623–4627)

      Xun Yuan, Bin Zhang, Zhentao Luo, Qiaofeng Yao, Prof. David Tai Leong, Prof. Ning Yan and Prof. Jianping Xie

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/anie.201311177

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      One, two … many: A novel NaOH-mediated NaBH4 reduction method was developed for the synthesis of mono-, bi-, and tri-thiolate-protected Au25 nanoclusters. Both the Au core and thiolate ligand surface can be precisely controlled.

    18. Metal–Organic Frameworks

      Stitching 2D Polymeric Layers into Flexible Interpenetrated Metal–Organic Frameworks within Single Crystals (pages 4628–4632)

      Zi-Xuan Zhang, Dr. Ni-Ni Ding, Dr. Wen-Hua Zhang, Prof. Jin-Xiang Chen, Prof. David J. Young and Prof. T. S. Andy Hor

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201311131

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      All stitched up: Dipyridyl ligands were found to diffuse into the channels in the crystal lattice of a two-dimensional polymeric complex. The absorbed dipyridyls thread through the pores of one layer and substitute the surface solvent molecules on the neighboring layers to stitch alternate layers to form flexible interpenetrated metal–organic frameworks (see picture).

    19. Main-Group Elements

      Catalytic Transfer Hydrogenation by a Trivalent Phosphorus Compound: Phosphorus-Ligand Cooperation Pathway or PIII/PV Redox Pathway? (pages 4633–4637)

      Dr. Guixiang Zeng, Prof. Dr. Satoshi Maeda, Prof. Dr. Tetsuya Taketsugu and Prof. Dr. Shigeyoshi Sakaki

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201311104

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      Team work: The title reaction of azobenzene with ammonia–borane using 1 occurs through a P-O cooperation mechanism, where the active species is 3. This mechanism is new for main-group-element compounds, and resembles the metal-ligand cooperation observed in transition-metal complexes. When azobenzene is absent, the PIII/PV redox process occurs during the isomerization of 3 into 2, but it is not involved in the catalytic transfer hydrogenation.

    20. Block Copolymerization

      Isoprene–Styrene Chain Shuttling Copolymerization Mediated by a Lanthanide Half-Sandwich Complex and a Lanthanidocene: Straightforward Access to a New Type of Thermoplastic Elastomers (pages 4638–4641)

      Dr. Andreia Valente, Dr. Gregory Stoclet, Dr. Fanny Bonnet, Prof. André Mortreux, Prof. Marc Visseaux and Prof. Philippe Zinck

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201311057

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      Chain shuttling copolymerization of isoprene and styrene using a borohydrido lanthane half-sandwich complex, a borohydrido ansa-neodymocene, and a magnesium dialkyl affords direct access to new amorphous thermoplastic elastomers. The resulting multiblock microstructure of soft and hard statistical copolymeric segments self-assembles at the nanoscale.

    21. Synthetic Methods

      Stereocontrolled Synthesis of syn-β-Hydroxy-α-Amino Acids by Direct Aldolization of Pseudoephenamine Glycinamide (pages 4642–4647)

      Dr. Ian B. Seiple, Jaron A. M. Mercer, Robin J. Sussman, Ziyang Zhang and Prof. Dr. Andrew G. Myers

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201400928

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      On aldol: Enolization of (R,R)- or (S,S)-pseudoephenamine glycinamide with lithium hexamethyldisilazide (LiHMDS) in the presence of LiCl followed by addition of either an aldehyde or ketone substrate affords aldol addition products which are stereochemically homologous with L- or D-threonine, respectively. These products can be obtained in stereoisomerically pure form in yields of 55–98 %, and are readily transformed into β-hydroxy-α-amino acids by mild hydrolysis or into 2-amino-1,3-diols by reduction.

    22. Dioxygen-Triggered Transannular Dearomatization of Benzo[5]helicene Diols: Highly Efficient Synthesis of Chiral π-Extended Diones (pages 4648–4651)

      Yun Shen, Prof. Hai-Yan Lu and Prof. Chuan-Feng Chen

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201400486

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      A bigger slice of π: In the title reaction, the helicity was successfully transferred into two quaternary all-carbon stereocenters of the π-extended diones. The optical resolution was easily achieved by column chromatography, and the absolute configurations were determined by X-ray analysis.

    23. Reaction Mechanisms

      Phenylalanine Ammonia Lyase Catalyzed Synthesis of Amino Acids by an MIO-Cofactor Independent Pathway (pages 4652–4656)

      Sarah L. Lovelock, Dr. Richard C. Lloyd and Prof. Nicholas J. Turner

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201311061

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      All manner of things: A competing MIO-independent (MIO=4-methylideneimidazole-5-one) reaction pathway has been identified for phenylalanine ammonia lyases (PALs), which proceeds in a non-stereoselective manner, resulting in the generation of D-phenylalanine derivatives. The mechanism of D-amino acid formation is explored through isotopic-labeling studies and mutagenesis of key active-site residues.

    24. C[BOND]S Bond Formation

      Gold-Catalyzed Intermolecular C[BOND]S Bond Formation: Efficient Synthesis of α-Substituted Vinyl Sulfones (pages 4657–4661)

      Yumeng Xi, Boliang Dong, Edward J. McClain, Qiaoyi Wang, Tesia L. Gregg, Dr. Novruz G. Akhmedov, Prof. Jeffrey L. Petersen and Prof. Xiaodong Shi

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201310142

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      Less basic, less hindered: The gold-catalyzed intermolecular Markovnikov addition of sulfinic acids to terminal alkynes has been achieved through the use of a bimetallic gold/gallium catalyst system. Various α-substituted vinyl sulfones were efficiently synthesized. A one-pot synthesis that starts from the bench-stable sodium sulfinates was also developed (DCE=1,2-dichloroethane).

    25. Chemical Protein Synthesis

      Total Chemical Synthesis of the Enzyme Sortase AΔN59 with Full Catalytic Activity (pages 4662–4666)

      Dr. Fang-Kun Deng, Dr. Liang Zhang, Dr. Ya-Ting Wang, Prof. Dr. Olaf Schneewind and Prof. Dr. Stephen B. H. Kent

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201310900

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      Just like the original: A fully convergent total synthesis of the enzyme sortase A from four unprotected peptide segments was established by using modern chemical ligation methods. The synthetic protein was of high purity, had correct mass, and had full enzymatic activity in a typical transpeptidation assay.

    26. Synthetic Methods

      Copper-Catalyzed Electrophilic Amination of Heteroarenes and Arenes by C[BOND]H Zincation (pages 4667–4670)

      Stacey L. McDonald, Charles E. Hendrick and Prof. Dr. Qiu Wang

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201311029

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      Direct amination of heteroarenes and arenes has been achieved in a one-pot zincation/Cu(OAc)2-catalyzed amination sequence using O-acylhydroxylamines. The method provides a rapid and efficient approach to a range of aromatic and heteroaromatic amines, including those which were previously inaccessible by using C[BOND]H amination methods. tmp=2,2,6,6-tetramethylpiperidide.

    27. Amino Acid Chemistry

      The Formation and Self-Assembly of Long Prebiotic Oligomers Produced by the Condensation of Unactivated Amino Acids on Oxide Surfaces (pages 4671–4674)

      Prof. Gianmario Martra, Dr. Chiara Deiana, Dr. Yuriy Sakhno, Ilvis Barberis, Marco Fabbiani, Dr. Marco Pazzi and Prof. Marco Vincenti

      Version of Record online: 24 FEB 2014 | DOI: 10.1002/anie.201311089

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      Prebiotic peptides: The catalytic formation from unactivated glycine vapor of poly-Gly up to 16 units long on a surface of SiO2 or TiO2 and the subsequent self-assembly of the polypeptides into closely packed aggregates upon contact with water has been observed. Both aspects can provide useful insights into the general problem of the surface reactivity of amino acids, and in particular, the prebiotic formation of biopolymers and their subsequent self-organization.

    28. Synthetic Methods

      Palladium Enolate Umpolung: Cyclative Diacetoxylation of Alkynyl Cyclohexadienones Promoted by a Pd/SPRIX Catalyst (pages 4675–4679)

      Dr. Kazuhiro Takenaka, Dr. Suman C. Mohanta and Prof. Dr. Hiroaki Sasai

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/anie.201311172

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      In a SPRIX: A new palladium-catalyzed reaction involving an unusual nucleophilic attack on a palladium enolate was developed using the SPRIX ligand. Treatment of alkynyl cyclohexadienone substrates with Pd/SPRIX in acetic acid under an oxygen atmosphere furnished diacetoxylated benzofuranone derivatives in good yields and with high enantioselectivity.

    29. Asymmetric Catalysis

      Catalytic Asymmetric Synthesis of [2,3]-Fused Indoline Heterocycles through Inverse-Electron-Demand Aza-Diels–Alder Reaction of Indoles with Azoalkenes (pages 4680–4684)

      Min-Chao Tong, Xuan Chen, Jun Li, Rong Huang, Haiyan Tao and Prof. Dr. Chun-Jiang Wang

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201400109

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      In(verse) demand: The unprecedented catalytic asymmetric inverse-electron-demand aza-Diels–Alder reaction of indoles with in situ formed azoalkenes is reported. A diverse set of [2,3]-fused indoline heterocycles were produced in generally good yields with high regioselectivity and diastereoselectivity, and with excellent enantioselectivity.

    30. Iron Catalysis

      Unprecedented Iron-Catalyzed Ester Hydrogenation. Mild, Selective, and Efficient Hydrogenation of Trifluoroacetic Esters to Alcohols Catalyzed by an Iron Pincer Complex (pages 4685–4689)

      Dr. Thomas Zell, Yehoshoa Ben-David and Prof. Dr. David Milstein

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201311221

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      The replacement of precious-metal catalysts by an iron complex was accomplished for the synthetically important, environmentally benign hydrogenation of esters to alcohols under mild conditions. The iron pincer complex (see scheme) selectively and efficiently catalyzes the hydrogenation of trifluoroacetates under remarkably mild conditions (5–25 bar and 40 °C).

    31. C[BOND]H Activation

      A Convenient Photocatalytic Fluorination of Unactivated C[BOND]H Bonds (pages 4690–4693)

      Shira D. Halperin, Hope Fan, Stanley Chang, Dr. Rainer E. Martin and Prof. Robert Britton

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201400420

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      The direct fluorination of unactivated C(sp3)[BOND]H bonds is catalyzed by the inexpensive photocatalyst tetrabutylammonium decatungstate (TBADT). This convenient reaction provides direct access to a wide range of fluorinated organic molecules, including structurally complex natural products, acyl fluorides, and fluorinated amino acids.

    32. Oligonucleotides

      Efficient Solid-Phase Synthesis of pppRNA by Using Product-Specific Labeling (pages 4694–4698)

      M. Goldeck, Prof. Dr. T. Tuschl, Prof. Dr. G. Hartmann and Dr. J. Ludwig

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201400672

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      Simple and straightforward: A strategy for the solid-phase synthesis and purification of 5′-triphosphate oligonucleotides through lipophilic tagging of the triphosphate moiety is reported. This method enables the efficient synthesis of 5′-triphosphorylated RNA derivatives and their gamma-phosphate-substituted analogues and will facilitate the advancement of therapeutic approaches that make use of 5′-triphosphate oligonucleotides as activators of the immune sensor RIG-I.

    33. Inorganic Lead(IV) Compound

      K4[PbSe4]⋅en⋅NH3: A Non-Oxide, Non-Halide Inorganic Lead(IV) Compound (pages 4699–4703)

      Dipl.-Chem. Günther Thiele, Thomas Krüger and Prof. Dr. Stefanie Dehnen

      Version of Record online: 20 MAR 2014 | DOI: 10.1002/anie.201310455

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      Against all odds: The first inorganic lead(IV) compound without oxygen, nitrogen, or halogen ligands attached to the lead atom was obtained upon solvothermal reaction of a phase with the nominal composition “K2PbSe2” in ethane-1,2-diamine (en). It contains the ortho-selenidoplumbate(IV) anion [PbIVSe4]4−, which, for reasons of relativistic effects on lead, is not intuitive; until now, tetrahedral [TE4]4− units (E=S, Se, Te) were only known for the lighter homologues T=Si, Ge, Sn.

    34. Polycyclic Bismuth Polyanion

      Formation of [Bi11]3−, A Homoatomic, Polycyclic Bismuth Polyanion, by Pyridine-Assisted Decomposition of [GaBi3]2− (pages 4704–4708)

      Dipl.-Chem. Bastian Weinert, Armin Rainer Eulenstein, Dr. Rodica Ababei and Prof. Dr. Stefanie Dehnen

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/anie.201310456

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      A bismuth “ufosan” sighted: Upon activation of [K([2.2.2]crypt)]2(GaBi3)⋅en by the solvent pyridine, [K([2.2.2]crypt)]3(Bi11)⋅2 py⋅tol was obtained as the first structurally characterized homoatomic, polycyclic bismuth polyanion. It has the [P11]3− “ufosan” structure. Spectroscopy, spectrometry, and DFT studies were employed to understand the unprecedented reaction and its (by-)products.

    35. Nanoswitches

      Bidirectional Chemical Communication between Nanomechanical Switches (pages 4709–4713)

      Susnata Pramanik, Soumen De and Prof. Dr. Michael Schmittel

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201400804

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      Life depends critically on information transfer, because ON-OFF regulation of biological machines requires error-free procedures for intra- and intercellular data exchange. Bidirectional molecular communication for the first time leads to a two-way information exchange between two nanomechanical switches within few minutes.

    36. Titanium Dioxide

      Charge Trapping at the Step Edges of TiO2 Anatase (101) (pages 4714–4716)

      Martin Setvin, Xianfeng Hao, Benjamin Daniel, Jiri Pavelec, Zbynek Novotny, Gareth S. Parkinson, Michael Schmid, Georg Kresse, Cesare Franchini and Ulrike Diebold

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/anie.201309796

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      In step: Step edges on the TiO2 anatase (101) surface act as exclusive charge trapping centers. While the electron trapping is not favorable at (101) terraces, it is possible at the steps. It results in a higher reactivity of the steps towards some adsorbates, as illustrated for the example of O2 adsorption.

    37. Protein–Protein Interactions

      You have full text access to this OnlineOpen article
      Cell-Permeant and Photocleavable Chemical Inducer of Dimerization (pages 4717–4720)

      Mirjam Zimmermann, Ruben Cal, Elia Janett, Viktor Hoffmann, Prof. Dr. Christian G. Bochet, Prof. Dr. Edwin Constable, Dr. Florent Beaufils and Prof. Dr. Matthias P. Wymann

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/anie.201310969

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      Effective transportation: The photocleavable chemical inducer of dimerization (CID) MeNV-HaXS allows the dynamic control of protein localization with high spatiotemporal and subcellular precision. MeNV-HaXS covalently links HaloTag- and SNAP-tag fusion proteins, making it possible to target selected intracellular organelles. Subsequent illumination cleaves MeNV-HaXS to liberate target proteins. Subcellular enzyme activities can be manipulated in this way.

    38. QM/MM for Metals

      Modeling Heat Dissipation at the Nanoscale: An Embedding Approach for Chemical Reaction Dynamics on Metal Surfaces (pages 4721–4724)

      Dr. Jörg Meyer and Prof. Dr. Karsten Reuter

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/anie.201400066

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      Hot or not: An embedding technique for metallic systems makes it possible to model energy dissipation into substrate phonons during surface chemical reactions from first principles. Application to O2 dissociation at Pd(100) predicts translationally “hot” oxygen adsorbates as a consequence of the released adsorption energy (ca. 2.6 eV). This calls into question the instant thermalization of reaction enthalpies generally assumed in heterogeneous catalysis modeling.

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